CN114852966A - Method and device for removing HF in fluorine gas - Google Patents
Method and device for removing HF in fluorine gas Download PDFInfo
- Publication number
- CN114852966A CN114852966A CN202110076695.1A CN202110076695A CN114852966A CN 114852966 A CN114852966 A CN 114852966A CN 202110076695 A CN202110076695 A CN 202110076695A CN 114852966 A CN114852966 A CN 114852966A
- Authority
- CN
- China
- Prior art keywords
- fluorine gas
- naf
- adsorbent
- temperature
- purification treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 114
- 239000011737 fluorine Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003463 adsorbent Substances 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000005406 washing Methods 0.000 claims abstract description 34
- 230000008929 regeneration Effects 0.000 claims abstract description 26
- 238000011069 regeneration method Methods 0.000 claims abstract description 25
- 238000009833 condensation Methods 0.000 claims abstract description 23
- 230000005494 condensation Effects 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 113
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 84
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 67
- 238000000746 purification Methods 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- 238000010926 purge Methods 0.000 claims description 35
- 238000005507 spraying Methods 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006073 displacement reaction Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000003507 refrigerant Substances 0.000 claims description 11
- 229920002313 fluoropolymer Polymers 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 230000005674 electromagnetic induction Effects 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000003518 caustics Substances 0.000 claims description 7
- 230000001172 regenerating effect Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 16
- 229910001873 dinitrogen Inorganic materials 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/20—Fluorine
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0003—Chemical processing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0054—Hydrogen halides
- C01B2210/0056—Hydrogen fluoride
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides a method and a device for removing HF in fluorine gas, wherein the method comprises the following steps: introducing fluorine gas prepared from an electrolytic cell into a condenser body, carrying out low-temperature primary condensation treatment to remove 90% of HF contained in the fluorine gas, introducing the fluorine gas subjected to condensation treatment into a purifier group, removing the HF in the fluorine gas by utilizing the chemical adsorption of a NaF adsorbent to the HF, carrying out high-temperature activation regeneration treatment on the NaF adsorbent after the adsorption capacity of the NaF adsorbent is saturated, and carrying out tail gas treatment on the fluorine gas and the HF generated in the regeneration process of the NaF adsorbent. The device comprises an electrolytic cell, a condenser group, a purifier group and a condenser group F 2 A gas collecting bottle, an emptying reactor, a primary water scrubber, an alkaline washing tower, a secondary water scrubber and an exhaust device. The invention has reasonable process, reasonable device structure, reliable operation performance and safety performance, and can realize continuous production and interlocking automatic control.
Description
Technical Field
The invention belongs to the field of fluorine chemical industry, and particularly relates to a method for removing HF in fluorine gas, and also relates to a device for removing HF in fluorine gas.
Background
Industrially, the method for producing fluorine gas by electrolysis comprises: the KF.2 HF (a mixture of potassium hydroxide and hydrogen fluoride) is electrolyzed by using compacted graphite as an anode, a steel electrolytic cell body as a cathode (or the anode adopts a carbon plate or a nickel plate, and the cathode adopts carbon steel), potassium hydrogen fluoride as electrolyte, anhydrous hydrofluoric acid is electrolyzed, and the anhydrous hydrofluoric acid is purified to obtain the KF.2 HF. The principle is as follows:
the general reaction formula of electrolysis: 2KHF 2 ＝2KF+H 2 +F 2 ↑ (1)
Anode: 2F - +2e - →F 2 (2)
Cathode: 2HF +2e - →H 2 +2F - (3)
The fluorine gas obtained by electrolyzing and preparing fluorine under the medium temperature condition (95-115 ℃) contains 3-5% of HF, and the content of HF in the fluorine gas still reaches 5000ppm (see the technical index of GB/T26251-2010) after the treatment of common methods and devices, and in order to meet the index that the content of HF in the fluorine gas for the electronic industry and semiconductors is less than or equal to 50ppm, the HF in the fluorine gas needs to be deeply removed under the specific process condition through a special method and a special device.
CN201710002091.6 mentions that a secondary cooling method is used for removing hydrogen fluoride in high-purity fluorine gas or high-purity fluorine-containing mixed gas, and the method comprises pressurizing the fluorine gas obtained by electrolysis or the fluorine-containing mixed gas prepared by fluorine gas obtained by electrolysis to positive pressure, filtering, and then sequentially carrying out primary condensation and secondary condensation; the temperature of the primary condensation is-60 to-100 ℃, and the temperature of the secondary condensation is-120 to-180 ℃. The purity of the fluorine gas product obtained by the method reaches more than 99.9 percent, and the fluorine gas product meets the requirements of the fluorine gas for the production of the existing electronic industry and fine chemical industry. The boiling point of pure fluorine gas is-188 ℃, and the method can cause the liquefaction of fluorine gas, is easy to cause safety accidents, and has certain potential safety hazards.
Disclosure of Invention
It is an object of the present invention to provide a method for removing HF from a fluorine gas, and it is another object of the present invention to provide an apparatus for removing HF from a fluorine gas.
Chemical reaction formulae or ion reaction formulae (4) to (8)) which may be related to the present invention:
NaF+HF＝NaHF 2 (4)
NaHF 2 ＝NaF+HF (5)
2H 2 O+2F 2 ＝4HF+O 2 (6)
2F 2 +C＝CF 4 (7)
HF+OH - ＝F - +H 2 O (8)
in order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention discloses a method for removing HF from fluorine gas, which comprises the following steps:
step A: preparing a material for adsorbing HF in fluorine gas according to the volume ratio of the pure nickel tube filler to the NaF adsorbent;
and B: carrying out low-temperature condensation treatment on the HF-containing fluorine gas generated by electrolysis to remove a first part of HF in the fluorine gas;
and C: adsorbing a second part of HF on the HF-containing fluorine gas subjected to low-temperature condensation treatment in the step B by using the NaF adsorbent in the material in the step A, and sequentially performing first purification treatment and second purification treatment to obtain purified fluorine gas;
step D: and C, when the adsorption capacity of the NaF adsorbent for adsorbing HF is saturated in the step C, heating, activating and regenerating the NaF adsorbent, and repeating the operation from the step B to the step C.
Preferably, the volume ratio of the pure nickel tube filler to the NaF adsorbent in the step A is 1: 8-1: 12, the low temperature in the step B is-80 to-70 ℃, and the temperature of the first purification treatment and the temperature of the second purification treatment in the step C are both 90-130 ℃.
Preferably, the step D specifically includes:
step D1: c, raising the temperature of the NaF adsorbent subjected to the first purification treatment and the second purification treatment in the step C to 250-400 ℃, reversely replacing and purging the NaF adsorbent subjected to the first purification treatment and the second purification treatment by using nitrogen, and cooling the NaF adsorbent to the ambient temperature;
step D2: reacting fluorine gas containing HF and carbon displaced by nitrogen after the NaF adsorbent is reversely displaced and purged by nitrogen in the step D1;
step D3: spraying HF in the reaction product of the step D2 with water for the first time, and detecting the concentration of the HF;
step D4: spraying residual HF treated in the step D3 with KOH or NaOH alkali liquor, and detecting the concentration of KOH or NaOH after spraying HF;
step D5: and D4, spraying residual HF for the second time by using water, detecting the concentration of the HF, and directly discharging the HF after the concentration of the HF meets the technical standard.
Preferably, the pressure of the nitrogen reverse displacement purging is 0.05-0.10 Mpa, the flow of the nitrogen reverse displacement purging is 5-40L/min, the time of the nitrogen reverse displacement purging is 8 hours, the reaction temperature in the step D2 is 200-250 ℃, and the concentration of KOH or NaOH alkali liquor in the step D4 is 8-20%.
The steps of the method for removing HF from fluorine gas will be described in detail below:
the materials in the step A comprise pure nickel tube filler and NaF adsorbent, wherein the pure nickel tube filler and the NaF adsorbent are filled in the pure nickel tube according to the volume ratio, so that the NaF adsorbent can adsorb HF in the fluorine gas in the pure nickel tube. The volume ratio of the pure nickel tube filler to the NaF adsorbent is preferably 1: 8-1: 12.
In the step B, the fluorine gas containing HF can be subjected to a low-temperature condensation treatment only once to remove the first part of HF in the fluorine gas to 90%, and the low-temperature condensation temperature in the process is preferably-80 to-70 ℃.
In the first purification treatment and the second purification treatment of the HF-containing fluorine gas in the step C, a second part of HF in the fluorine gas can be adsorbed by the NaF adsorbent in the step A. Can occur in the adsorption process of NaF adsorbent
NaF+HF＝NaHF 2 (4)
In the adsorption reaction, a Fourier transform infrared absorption spectrometer (FTIR) is used to detect that the concentration of HF in the fluorine gas after the first purification treatment and the second purification treatment is not more than 50ppm, and the temperature of the first purification treatment and the temperature of the second purification treatment are both preferably 90-130 ℃.
In step D, the capacity of the NaF adsorbent to adsorb HF is saturated at all times, and HF cannot be adsorbed continuously, so that the NaF adsorbent needs to be activated by heating to allow the NaF adsorbent to be regenerated for use, and after the NaF adsorbent is regenerated, the operations in steps B to C can be repeated to continuously adsorb HF in the fluorine gas. Regeneration of the NaF adsorbent occurs
NaHF 2 ＝NaF+HF (5)
The desorption reaction of (1).
In the step D1, the NaF adsorbent subjected to the first purification treatment and the second purification treatment is subjected to reverse displacement purging with nitrogen gas, so that the fluorine gas and HF present in the NaF adsorbent can be displaced together with the nitrogen gas, in the process, the pressure of the reverse displacement purging with nitrogen gas is preferably 0.05 to 0.10Mpa, the flow rate of the reverse displacement purging with nitrogen gas is preferably 5 to 40L/min, and the time of the reverse displacement purging with nitrogen gas is preferably 8 hours.
In the step D2, the fluorine gas and HF which are replaced with the nitrogen gas in the step D1 are used, and in the present invention, the fluorine gas and the raw material carbon are brought into contact with each other by utilizing the principle that the raw material carbon can react with the fluorine gas, and the raw material carbon is dehydrated at a high temperature of 100 to 150 ℃, so that the fluorine gas and the raw material carbon are generated
2F 2 +C＝CF 4 (7)
If the raw material carbon is not subjected to dehydration treatment at a high temperature of 100 to 150 ℃, the reaction of (1) occurs
2H 2 O+2F 2 ＝4HF+O 2 (6)
The violent reaction has potential safety hazards, and the reaction temperature of the fluorine gas and the raw material carbon is preferably 200-250 ℃.
Since HF is still present in the reaction product of step D2, the concentration of HF can be diluted by spraying the HF in the reaction product of step D2 with water in step D3, during which the concentration of HF after the first spray with water is detected by fourier transform infrared absorption spectroscopy (FTIR), and when the detected concentration of HF is between 10 and 50ppm, the spraying of HF in the reaction product of step D2 is continued with fresh water until the detected concentration of HF is not greater than 10ppm before the next step can be performed.
In step D4, spraying KOH or NaOH solution on the HF remaining after the treatment in step D3
HF+OH - ＝F - +H 2 O (8)
The method utilizes the principle of acid-base neutralization to effectively absorb HF by using KOH or NaOH alkali liquor, samples and detects the concentration of KOH or NaOH after the KOH or NaOH alkali liquor is sprayed with the HF, when the detected concentration of the KOH or NaOH is not less than 2%, uses new KOH or NaOH alkali liquor to continuously spray the residual HF in the step D3 until the detected concentration of the KOH or NaOH is less than 2%, and the concentration of the KOH or NaOH alkali liquor is preferably 8-20% in the process.
And D5, spraying the HF remained after the treatment of the step D4 with water, diluting the concentration of the HF, detecting the concentration of the HF after the second spraying with water by using a Fourier transform infrared absorption spectrometer (FTIR), and when the detected concentration of the HF is between 5 and 10ppm, continuously spraying the HF in the reaction product of the step D2 with new water until the detected concentration of the HF is not more than 5ppm, so that the HF can not be directly discharged.
The device for removing HF in fluorine gas comprises an electrolytic cell, a condenser group and a purifier group, wherein the electrolytic cell is connected with the condenser group, the condenser group comprises a condenser body, a refrigerant system and a refrigerant pump, the top of the condenser body is connected with the purifier group, the purifier group comprises a first purifier group and a second purifier group which have the same structure, and the first purifier group comprises F 2 An intake valve, said F 2 The admission valve is connected regeneration discharge valve and one-level clarifier respectively, the vertical insertion of one-level clarifier runs through first electromagnetic induction heater, establish first pure nickel pipe in the one-level clarifier, the second grade clarifier is connected at one-level clarifier top, the vertical insertion of second grade clarifier runs through second electromagnetic induction heater, establish the pure nickel pipe of second in the second grade clarifier, regeneration valve and F are connected respectively at second grade clarifier top 2 Outlet valve, the regeneration replacement valve being connected to N 2 Bottle, said F 2 The outlet valve is respectively connected with a system purging emptying valve and an F 2 The system comprises a gas collecting bottle, a system purging vent valve, a vent reactor, a first-stage water washing tower, a first corrosion-resistant water circulating pump, a first fluoroplastic barrel, an alkaline washing tower, an alkaline circulating pump and a system purging vent valve, wherein the top of the vent reactor is connected with the first-stage water washing tower, the bottom of the first-stage water washing tower is connected with the first corrosion-resistant water circulating pump, the side surface of the first-stage water washing tower, which is the same as the side surface where the first corrosion-resistant water circulating pump is located, is connected with the first fluoroplastic barrel, the top of the first-stage water washing tower is connected with the alkaline washing tower, the bottom of the alkaline washing tower is connected with the alkaline circulating pump, and the alkaline washing tower, which is located with the alkaline circulating pump, is connected with the alkaline circulating pumpThe waste alkali liquor barrel is connected with the same side face, the top of the alkali washing tower is connected with the second-stage water washing tower, the bottom of the second-stage water washing tower is connected with the second corrosion-resistant water circulating pump, the side face, identical to the second corrosion-resistant water circulating pump, of the second-stage water washing tower is connected with the second fluoroplastic barrel, and the top of the second-stage water washing tower is connected with the exhaust device.
As a preferable technical scheme, a first thermometer is inserted from the bottom of the primary purifier, the first thermometer is introduced into a first pure nickel pipe, a second thermometer is inserted from the bottom of the secondary purifier, and the second thermometer is introduced into a second pure nickel pipe.
Preferably, the first thermometer is connected to a first temperature sensor, and the second thermometer is connected to a second temperature sensor.
Preferably, the bottom of the first thermometer and the bottom of the second thermometer are connected with a control PLC together.
As a preferred technical scheme, a first pressure gauge is installed on the first-stage purifier, and a second pressure gauge is installed on the second-stage purifier.
As a preferable technical scheme, the control PLC is provided with a control switch, a low-temperature key, a high-temperature key and a regeneration key.
The invention has at least the following beneficial effects:
1) the method can remove HF in the fluorine gas, so that the concentration of the HF in the fluorine gas is controlled to be not more than 50ppm, thereby improving the purity of the fluorine gas;
2) the NaF adsorbent used in the method can be regenerated for reuse and HF can be removed in the regeneration desorption process of the NaF adsorbent;
3) the HF in the method adopts the processes of water washing, alkali washing and water washing again, so that the consumption of alkali solution KOH or NaOH can be reduced, and the treatment capacity and material consumption of a sewage treatment process can be reduced.
4) The device can remove 90% of HF in fluorine gas by only one-time condensation in the condenser body, and the control PLC can adjust and control the temperature of the first-stage purifier and the second-stage purifier and can also control and complete the regeneration of NaF adsorbents in the second pure nickel tube and the first pure nickel tube.
5) The device can be used for treating tail gas of fluorine gas and HF generated in the regeneration process of the NaF adsorbent, the tail gas is leached and purified after sequentially passing through the primary water washing tower, the alkaline washing tower and the secondary water washing tower, and the tail gas can be discharged into the air after entering the exhaust device without polluting the environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments will be briefly introduced below, it is obvious that the drawings in the following description are only exemplary embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without inventive effort, wherein:
FIG. 1 is a schematic view showing the structure of an apparatus for removing HF from a fluorine gas according to the present invention.
The reference numerals include:
i, a first purifier group II and a second purifier group
1, an electrolytic cell 2, a condenser body 3, a refrigerant system 4, a first valve 5, a refrigerant pump 6, a second valve
7:F 2 An air inlet valve 8, a regeneration exhaust valve 9, a primary purifier 10, a first electromagnetic induction heater 11, a first pure nickel pipe 12, a first thermometer 13, a first temperature sensor 14, a first pressure gauge 15, a control PLC 151, a control switch 152, a low temperature key 153, a high temperature key 154, a regeneration key 16, a secondary purifier 17, a second electromagnetic induction heater 18, a second pure nickel pipe 19, a second thermometer 20, a second temperature sensor 21, a second pressure gauge 22, a regeneration replacement valve 23, a F 2 Outlet valve 24: N 2 Bottle 25 third valve 26F 2 A gas collecting bottle 27, a system purging vent valve 28, a vent reactor 29, a primary water washing tower 30, a first corrosion-resistant water circulating pump 31, a first fluoroplastic barrel 32, an alkaline washing tower 33, an alkaline circulating pump 34, a waste alkali liquid barrel 35, a secondary water washing tower 36, a second corrosion-resistant water circulating pump 37, a second fluoroplastic barrel 38 and an exhaust device.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are only exemplary embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A method for removing HF from fluorine gas, comprising the steps of:
step A: preparing a material for adsorbing HF in the fluorine gas according to the volume ratio of the pure nickel tube filler to the NaF adsorbent of 1: 6.8;
and B: carrying out low-temperature condensation treatment at-90 ℃ on HF-containing fluorine gas generated by electrolysis to remove a first part of HF in the fluorine gas;
and C: adsorbing a second part of HF on the HF-containing fluorine gas subjected to the low-temperature condensation treatment at the temperature of-90 ℃ in the step B by using the NaF adsorbent in the material in the step A, and sequentially performing first purification treatment and second purification treatment at the temperature of 80 ℃ to obtain purified fluorine gas;
step D: and C, when the adsorption capacity of the NaF adsorbent for adsorbing HF is saturated in the step C, heating, activating and regenerating the NaF adsorbent, and repeating the operation from the step B to the step C.
Step D1: c, heating the temperature of the NaF adsorbent subjected to the first purification treatment and the second purification treatment in the step C to 250-400 ℃, reversely displacing and purging the NaF adsorbent subjected to the first purification treatment and the second purification treatment by using nitrogen at the flow rate of 10L/min and the pressure of 0.03MPa, cooling the NaF adsorbent to the ambient temperature, and keeping the whole reverse displacement and purging time of the nitrogen for 7 hours;
step D2: reacting fluorine gas containing HF and carbon displaced with nitrogen gas after reversely displacing and purging the NaF adsorbent by nitrogen gas in the step D1 at a temperature of 180 ℃;
step D3: spraying HF in the reaction product of the step D2 with water for the first time, and detecting the concentration of the HF;
step D4: spraying residual HF treated in the step D3 with 6% KOH alkali liquor, and detecting the concentration of KOH after spraying the HF;
step D5: and D4, spraying residual HF for the second time by using water, detecting the concentration of the HF, and directly discharging the HF after the concentration of the HF meets the technical standard.
In this example, the concentration of HF in the fluorine gas after the first purification treatment and the second purification treatment in step C was finally detected by a fourier transform infrared absorption spectrometer (FTIR) to be 128ppm, the concentration of HF detected in step D3 was 74ppm, the concentration of HF detected in step D5 was 53ppm, and the concentration of KOH detected in step D4 was 5.1%.
Example two
A method for removing HF from fluorine gas, comprising the steps of:
step A: preparing a material for adsorbing HF in the fluorine gas according to the volume ratio of the pure nickel tube filler to the NaF adsorbent of 1: 14.6;
and B: carrying out low-temperature condensation treatment at-65 ℃ on HF-containing fluorine gas generated by electrolysis to remove a first part of HF in the fluorine gas;
and C: adsorbing a second part of HF on the HF-containing fluorine gas subjected to low-temperature condensation treatment at-65 ℃ in the step B by using the NaF adsorbent in the material in the step A, and performing primary purification treatment and secondary purification treatment at 150 ℃ to obtain purified fluorine gas;
step D: and C, when the adsorption capacity of the NaF adsorbent for adsorbing HF is saturated in the step C, heating, activating and regenerating the NaF adsorbent, and repeating the operation from the step B to the step C.
Step D1: c, heating the temperature of the NaF adsorbent subjected to the first purification treatment and the second purification treatment in the step C to 250-400 ℃, reversely displacing and purging the NaF adsorbent subjected to the first purification treatment and the second purification treatment by using nitrogen at a flow rate of 45L/min and a pressure of 0.15Mpa, cooling the NaF adsorbent to an ambient temperature, and continuously purging for 12.5 hours by using the reverse displacement of the nitrogen;
step D2: reacting fluorine gas containing HF and carbon displaced with nitrogen gas after reversely displacing and purging the NaF adsorbent with nitrogen gas in step D1 at a temperature of 300 ℃;
step D3: spraying HF in the reaction product of the step D2 with water for the first time, and detecting the concentration of the HF;
step D4: spraying residual HF treated in the step D3 with 25% NaOH alkali liquor, and detecting the concentration of NaOH after spraying HF;
step D5: and D4, spraying residual HF for the second time by using water, detecting the concentration of the HF, and directly discharging the HF after the concentration of the HF meets the technical standard.
In the second example, the concentration of HF in the fluorine gas after the first purification treatment and the second purification treatment in step C was finally detected by a fourier transform infrared absorption spectrometer (FTIR) to be 165ppm, the concentration of HF detected in step D3 to be 82ppm, the concentration of HF detected in step D5 to be 65ppm, and the concentration of NaOH detected in step D4 to be 15%.
EXAMPLE III
A method for removing HF from fluorine gas, comprising the steps of:
step A: preparing a material for adsorbing HF in fluorine gas according to the volume ratio of the pure nickel tube filler to the NaF adsorbent being 1: 8;
and B, step B: carrying out low-temperature condensation treatment at-80 ℃ on HF-containing fluorine gas generated by electrolysis to remove a first part of HF in the fluorine gas;
and C: adsorbing a second part of HF on the HF-containing fluorine gas subjected to the low-temperature condensation treatment at minus 80 ℃ in the step B by using the NaF adsorbent in the material in the step A, and performing first purification treatment and second purification treatment at the temperature of 90 ℃ to obtain purified fluorine gas;
step D: and C, when the adsorption capacity of the NaF adsorbent for adsorbing HF is saturated in the step C, heating, activating and regenerating the NaF adsorbent, and repeating the operation from the step B to the step C.
Step D1: c, heating the temperature of the NaF adsorbent subjected to the first purification treatment and the second purification treatment in the step C to 250-400 ℃, reversely displacing and purging the NaF adsorbent subjected to the first purification treatment and the second purification treatment by using nitrogen at the flow rate of 30L/min and the pressure of 0.05Mpa, cooling the NaF adsorbent to the ambient temperature, and keeping the whole reverse displacement and purging time of the nitrogen for 8 hours;
step D2: reacting fluorine gas containing HF and carbon displaced with nitrogen gas after reversely displacing and purging the NaF adsorbent with nitrogen gas in step D1 at a temperature of 200 ℃;
step D3: spraying HF in the reaction product of the step D2 with water for the first time, and detecting the concentration of the HF;
step D4: spraying residual HF treated in the step D3 with 8% KOH alkali liquor, and detecting the concentration of KOH after spraying the HF;
step D5: and D, spraying the residual HF treated in the step D4 with water for the second time, and detecting the concentration of the HF, wherein the HF is directly discharged after the concentration of the HF meets the technical standard.
In this example, the concentration of HF in the fluorine gas after the first purification treatment and the second purification treatment in step C was 37ppm, the concentration of HF detected in step D3 was 9ppm, the concentration of HF detected in step D5 was 4.8ppm, and the concentration of KOH detected in step D4 was 1.8% as measured by fourier transform infrared absorption spectrometer (FTIR).
Example four
A method for removing HF from fluorine gas, comprising the steps of:
step A: preparing a material for adsorbing HF in fluorine gas according to the volume ratio of the pure nickel tube filler to the NaF adsorbent of 1: 12;
and B: carrying out low-temperature condensation treatment at-70 ℃ on HF-containing fluorine gas generated by electrolysis to remove a first part of HF in the fluorine gas;
and C: adsorbing a second part of HF on the HF-containing fluorine gas subjected to the low-temperature condensation treatment at minus 70 ℃ in the step B by using the NaF adsorbent in the material in the step A, and performing first purification treatment and second purification treatment at the temperature of 130 ℃ to obtain purified fluorine gas;
step D: and C, when the adsorption capacity of the NaF adsorbent for adsorbing HF is saturated in the step C, heating, activating and regenerating the NaF adsorbent, and repeating the operation from the step B to the step C.
Step D1: c, heating the temperature of the NaF adsorbent subjected to the first purification treatment and the second purification treatment in the step C to 250-400 ℃, reversely displacing and purging the NaF adsorbent subjected to the first purification treatment and the second purification treatment by using nitrogen at a flow rate of 28L/min and a pressure of 0.10Mpa, cooling the NaF adsorbent to an ambient temperature, and continuously purging for 8 hours by using the reverse displacement of the nitrogen;
step D2: reacting fluorine gas containing HF and carbon displaced with nitrogen gas after reversely displacing and purging the NaF adsorbent by nitrogen gas in the step D1 at a temperature of 250 ℃;
step D3: spraying HF in the reaction product of the step D2 with water for the first time, and detecting the concentration of the HF;
step D4: spraying residual HF treated in the step D3 with 20% NaOH alkali liquor, and detecting the concentration of NaOH after spraying HF;
step D5: and D4, spraying residual HF for the second time by using water, detecting the concentration of the HF, and directly discharging the HF after the concentration of the HF meets the technical standard.
In this example, the concentration of HF in the fluorine gas after the first purification treatment and the second purification treatment in step C was finally measured by Fourier transform Infrared absorption Spectroscopy (FTIR) to be 32ppm, the concentration of HF measured in step D3 was 7ppm, the concentration of HF measured in step D5 was 3.6ppm, and the concentration of NaOH measured in step D4 was 1.3%.
EXAMPLE five
A method for removing HF from fluorine gas, comprising the steps of:
step A: preparing a material for adsorbing HF in the fluorine gas according to the volume ratio of the pure nickel tube filler to the NaF adsorbent of 1: 10.5;
and B: carrying out low-temperature condensation treatment at-75 ℃ on HF-containing fluorine gas generated by electrolysis to remove a first part of HF in the fluorine gas;
and C: adsorbing a second part of HF on the HF-containing fluorine gas subjected to low-temperature condensation treatment at the temperature of-75 ℃ in the step B by using the NaF adsorbent in the material in the step A, and sequentially performing first purification treatment and second purification treatment at the temperature of 110 ℃ to obtain purified fluorine gas;
step D: and C, when the adsorption capacity of the NaF adsorbent for adsorbing HF is saturated in the step C, heating, activating and regenerating the NaF adsorbent, and repeating the operation from the step B to the step C.
Step D1: c, heating the temperature of the NaF adsorbent subjected to the first purification treatment and the second purification treatment in the step C to 250-400 ℃, reversely displacing and purging the NaF adsorbent subjected to the first purification treatment and the second purification treatment by using nitrogen at a flow rate of 22L/min and a pressure of 0.08Mpa, cooling the NaF adsorbent to an ambient temperature, and keeping the total reverse displacement and purging time of the nitrogen for 8 hours;
step D2: reacting fluorine gas containing HF and carbon displaced with nitrogen gas after reversely displacing and purging the NaF adsorbent with nitrogen gas in the step D1 at a temperature of 220 ℃;
step D3: spraying HF in the reaction product of the step D2 with water for the first time, and detecting the concentration of the HF;
step D4: spraying residual HF treated in the step D3 with 12% KOH alkali liquor, and detecting the concentration of KOH after spraying the HF;
step D5: and D4, spraying residual HF for the second time by using water, detecting the concentration of the HF, and directly discharging the HF after the concentration of the HF meets the technical standard.
In this example, the fluorine gas obtained by the first purification treatment and the second purification treatment in step C was finally detected by a Fourier transform infrared absorption spectrometer (FTIR) to have an HF concentration of 21ppm, an HF concentration of 6.4ppm in step D3, an HF concentration of 2ppm in step D5, and a KOH concentration of 0.5% in step D4.
EXAMPLE six
As shown in fig. 1, the apparatus for removing HF from fluorine gas according to the first to fifth embodiments of the present invention includes an electrolytic cell 1, a condenser set, and a purifier set, the electrolytic cell 1 is connected to the condenser set, the condenser set includes a condenser body 2, a refrigerant system 3, and a refrigerant pump 5, a first valve 4 is installed between the refrigerant system 3 and the refrigerant pump 5, a second valve 6 is installed between the condenser body 2 and the refrigerant pump 5, the top of the condenser body 2 is connected to the purifier set, the purifier set includes a first purifier set i and a second purifier set ii having the same structure, the first purifier set i includes F 2 Inlet valve 7, F 2 The air inlet valve 7 is respectively connected with a regeneration exhaust valve 8 and a first-stage purifier 9, and the first-stage purifier 9 is vertically inserted and penetratedA first electromagnetic induction heater 10 is penetrated, a first pure nickel pipe 11 is arranged in a first-stage purifier 9, materials are filled in the first pure nickel pipe 11 according to the volume ratio of pure nickel pipe filler to NaF adsorbent of 1: 8-1: 12, a second-stage purifier 16 is connected to the top of the first-stage purifier 9, the second-stage purifier 16 is vertically inserted into and penetrates through a second electromagnetic induction heater 17, a second pure nickel pipe 18 is arranged in the second-stage purifier 16, materials are filled in the second pure nickel pipe 18 according to the volume ratio of pure nickel pipe filler to NaF adsorbent of 1: 8-1: 12, and the top of the second-stage purifier 16 is respectively connected with a regeneration replacement valve 22 and an F 2 An outlet valve 23, a regeneration replacement valve 22 are connected to N 2 Bottle 24, F 2 The outlet valve 23 is connected to the system purge vent valve 27 and F, respectively 2 Gas collecting bottle 26, F 2 Outlet valves 23 and F 2 A third valve 25 is installed between the gas collecting bottles 26, the system purging and emptying valve 27 is connected with an emptying reactor 28, the top of the emptying reactor 28 is connected with a primary water scrubber 29, the bottom of the primary water scrubber 29 is connected with a first corrosion-resistant water circulating pump 30, the side surface of the primary water scrubber 29, which is the same as the side surface where the first corrosion-resistant water circulating pump 30 is located, is connected with a first fluoroplastic barrel 31, the top of the primary water scrubber 29 is connected with a caustic tower 32, the bottom of the caustic tower 32 is connected with an alkali-resistant circulating pump 33, the side surface of the caustic tower 32, which is the same as the side surface where the alkali-resistant circulating pump 33 is located, is connected with a waste lye barrel 34, the top of the caustic tower 32 is connected with a secondary water scrubber 35, the bottom of the secondary water scrubber 35 is connected with a second corrosion-resistant water circulating pump 36, the side surface of the secondary water scrubber 35, which is the same as the side surface where the second corrosion-resistant water circulating pump 36 is located, is connected with a second fluoroplastic barrel 37, and the top of the secondary water scrubber 35 is connected with an exhaust device 38.
Preferably, a first thermometer 12 is inserted from the bottom of the primary purifier 9, the first thermometer 12 leads into a first pure nickel pipe 11, a second thermometer 19 is inserted from the bottom of the secondary purifier 16, and the second thermometer 19 leads into a second pure nickel pipe 18. The first thermometer 12 may detect a real-time temperature inside the first pure nickel tube 11, and the second thermometer 19 may detect a real-time temperature inside the second pure nickel tube 18.
Preferably, the first thermometer 12 is connected to the first temperature sensor 13, and the second thermometer 19 is connected to the second temperature sensor 20. The first thermometer 12 transmits the real-time temperature in the first pure nickel tube 11 to the first temperature sensor 13, and the second thermometer 19 transmits the real-time temperature in the second pure nickel tube 18 to the second temperature sensor 20.
Preferably, the bottom of the first thermometer 12 and the bottom of the second thermometer 19 are connected together to the control PLC 15. The control PLC 15 can regulate and control the temperature in the primary purifier 9 and the secondary purifier 16.
Preferably, the first purifier 9 is provided with a first pressure gauge 14, and the second purifier 16 is provided with a second pressure gauge 21. A first pressure gauge 14 may sense the pressure in the primary purifier 9 and a second pressure gauge 21 may sense the pressure in the secondary purifier 16.
Preferably, the control PLC 15 is provided with a control switch 151, a low temperature key 152, a high temperature key 153, and a regeneration key 154. The control switch 151 can start and stop the operation of the purifier group, the low temperature key 152 and the high temperature key 153 can adjust the temperature according to the temperature conditions in the first-stage purifier 9 and the second-stage purifier 16, and the regeneration key 154 can control the regeneration program of the NaF adsorbent in the second pure nickel pipe 18, so that the NaF adsorbent can be regenerated and used.
In a different embodiment, the condenser group is disposed downstream of the electrolytic cell 1, the first purifier group i is disposed downstream of the condenser group, the blowdown reactor 28 is disposed downstream of the first purifier group i, the primary water scrubber 29 is disposed downstream of the blowdown reactor 28, the caustic scrubber 32 is disposed downstream of the primary water scrubber 29, and the secondary water scrubber 35 is disposed downstream of the caustic scrubber 32, that is, after 90% of HF contained in the HF-containing fluorine gas generated by electrolysis of the electrolytic cell 1 is removed from the condenser body 2 in the condenser group, the HF-containing fluorine gas enters the primary purifier 9 and the secondary purifier 16 in the first purifier group i in sequence to be purified to obtain purified fluorine gas, and after purification in the primary purifier 9 and the secondary purifier 16 is completed, the N is opened 2 The bottle 24 and the regeneration replacement valve 22 can control and adjust the regeneration of the NaF adsorbent in the first pure nickel tube 11 and the second pure nickel tube 18 through the control PLC 15, HF and fluorine gas generated in the regeneration process enter the emptying reactor 28 to react, the HF enters the primary water washing tower 29 after the reaction is completed and is washed by water, the HF enters the alkaline tower 32 and is washed by alkaline liquor, and finally the HF enters the secondary water washing tower 35 and is washed by water again, so that the HF is purified and then enters the exhaust device 38.
In the implementation process, when the first purifier group I can not work continuously, the second purifier group II with the same structure as the first purifier group I can be used instead, and the work is guaranteed to continue.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the present invention may be made by those skilled in the art without departing from the principle of the present invention, and such modifications and embellishments should also be considered as within the scope of the present invention.
Claims (10)
1. A method for removing HF from fluorine gas is characterized in that: the method comprises the following steps:
step A: preparing a material for adsorbing HF in fluorine gas according to the volume ratio of the pure nickel tube filler to the NaF adsorbent;
and B, step B: carrying out low-temperature condensation treatment on the HF-containing fluorine gas generated by electrolysis to remove a first part of HF in the fluorine gas;
and C: b, adsorbing a second part of HF on the fluorine gas subjected to low-temperature condensation treatment and removing the first part of HF in the fluorine gas by using the NaF adsorbent in the material in the step A, and performing first purification treatment and second purification treatment in sequence to obtain purified fluorine gas;
step D: and C, when the adsorption capacity of the NaF adsorbent for adsorbing HF is saturated in the step C, heating, activating and regenerating the NaF adsorbent, and repeating the operation from the step B to the step C.
2. The method according to claim 1, wherein said fluorine gas is removed from HF by a method comprising the steps of: the volume ratio of the pure nickel tube filler to the NaF adsorbent in the step A is 1: 8-1: 12, the low temperature in the step B is-80 to-70 ℃, and the temperature of the first purification treatment and the temperature of the second purification treatment in the step C are both 90-130 ℃.
3. The method according to claim 1 or 2, wherein the fluorine gas is removed from HF by the following steps: the step D specifically comprises the following steps:
step D1: c, raising the temperature of the NaF adsorbent subjected to the first purification treatment and the second purification treatment in the step C to 250-400 ℃, reversely replacing and purging the NaF adsorbent subjected to the first purification treatment and the second purification treatment by using nitrogen, and cooling the NaF adsorbent to the ambient temperature;
step D2: reacting fluorine gas containing HF and carbon displaced by nitrogen after the NaF adsorbent is reversely displaced and purged by nitrogen in the step D1;
step D3: spraying HF in the reaction product of the step D2 with water for the first time, and detecting the concentration of the HF;
step D4: spraying residual HF treated in the step D3 with KOH or NaOH alkali liquor, and detecting the concentration of KOH or NaOH after spraying HF;
step D5: and D4, spraying residual HF for the second time by using water, detecting the concentration of the HF, and directly discharging the HF after the concentration of the HF meets the technical standard.
4. The method according to claim 3, wherein said fluorine gas is removed from HF by a method comprising the steps of: the pressure of the nitrogen reverse displacement purging is 0.05-0.10 Mpa, the flow of the nitrogen reverse displacement purging is 5-40L/min, the time of the nitrogen reverse displacement purging is 8 hours, the reaction temperature in the step D2 is 200-250 ℃, and the concentration of KOH or NaOH alkali liquor in the step D4 is 8-20%.
5. An apparatus for removing HF from fluorine gas, comprising: including electrolytic cell (1), condenser group, clarifier group, electrolytic cell (1) is connected condenser group, condenser group includes condenser body (2), refrigerant system (3) and refrigerant pump (5), condenser body (2) top is connected clarifier group, clarifier group includes two first clarifier group (I) and second clarifier group (II) that the structure is the same, first clarifier group (I) includes F 2 An intake valve (7), F 2 The air inlet valve (7) is respectively connected with a regeneration exhaust valve (8) and a first-stage purifier (9), and the first-stage purifier (9) is vertically inserted and connectedRun through first electromagnetic induction heater (10), establish first pure nickel pipe (11) in first-order clarifier (9), second grade clarifier (16) is connected at first-order clarifier (9) top, second grade clarifier (16) vertical insertion and run through second electromagnetic induction heater (17), establish second pure nickel pipe (18) in second grade clarifier (16), regeneration replacement valve (22) and F are connected respectively at second grade clarifier (16) top 2 An outlet valve (23), the regeneration replacement valve (22) being connected to N 2 Bottle (24), said F 2 The outlet valve (23) is respectively connected with a system purging blow-down valve (27) and an F 2 Gas collection bottle (26), system purge blow-down valve (27) is connected with blow-down reactor (28), one-level washing tower (29) is connected at blow-down reactor (28) top, first anti-corrosive water circulating pump (30) is connected at the bottom of one-level washing tower (29) the side of one-level washing tower (29) the same as first anti-corrosive water circulating pump (30) locates connects first fluoroplastic bucket (31), alkaline tower (32) is connected at the top of one-level washing tower (29) the top of one-level washing tower, alkaline-resisting circulating pump (33) is connected at the bottom of alkaline tower (32) the side of alkaline tower (32) the same as alkaline-resisting circulating pump (33) locates connects spent caustic lye bucket (34), second anti-corrosive water circulating pump (36) is connected at the top of alkaline tower (32), second anti-corrosive water circulating pump (36) is connected at the bottom of second-level washing tower (35) the side of second-level washing tower (35) the same as second anti-corrosive water circulating pump (36) locates links And a second fluoroplastic barrel (37) is connected, and the top of the secondary water washing tower (35) is connected with an exhaust device (38).
6. The apparatus according to claim 5, wherein said apparatus comprises: a first thermometer (12) is inserted from the bottom of the primary purifier (9), the first thermometer (12) leads into a first pure nickel pipe (11), a second thermometer (19) is inserted from the bottom of the secondary purifier (16), and the second thermometer (19) leads into a second pure nickel pipe (18).
7. The apparatus according to claim 6, wherein said apparatus comprises: the first thermometer (12) is connected with a first temperature sensor (13), and the second thermometer (19) is connected with a second temperature sensor (20).
8. The apparatus according to claim 6 or 7, wherein: the bottom of the first thermometer (12) and the bottom of the second thermometer (19) are jointly connected with a control PLC (15).
9. The apparatus according to claim 5, wherein said apparatus comprises: the first-stage purifier (9) is provided with a first pressure gauge (14), and the second-stage purifier (16) is provided with a second pressure gauge (21).
10. The apparatus according to claim 8, wherein said apparatus comprises: the control PLC (15) is attached with a control switch (151), a low-temperature key (152), a high-temperature key (153) and a regeneration key (154).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110076695.1A CN114852966B (en) | 2021-01-20 | 2021-01-20 | Method and device for removing HF in fluorine gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110076695.1A CN114852966B (en) | 2021-01-20 | 2021-01-20 | Method and device for removing HF in fluorine gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114852966A true CN114852966A (en) | 2022-08-05 |
| CN114852966B CN114852966B (en) | 2024-08-13 |
Family
ID=82623138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110076695.1A Active CN114852966B (en) | 2021-01-20 | 2021-01-20 | Method and device for removing HF in fluorine gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114852966B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115571859A (en) * | 2022-11-10 | 2023-01-06 | 中核四0四有限公司 | Method and device for reducing content of hydrogen fluoride in fluorine gas |
| CN115650174A (en) * | 2022-11-01 | 2023-01-31 | 福建德尔科技股份有限公司 | Purification device for high-purity fluorine gas |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007301467A (en) * | 2006-05-11 | 2007-11-22 | Hitachi Ltd | Method and apparatus for treating fluorine compound contained in gas |
| CN101423195A (en) * | 2008-11-17 | 2009-05-06 | 袁翔云 | Purification method of fluorine gas |
| WO2012016997A1 (en) * | 2010-08-05 | 2012-02-09 | Solvay Sa | Method for the purification of fluorine |
| CN102963870A (en) * | 2012-12-11 | 2013-03-13 | 中昊晨光化工研究院有限公司 | Method for purifying fluorine gas |
| CN105214330A (en) * | 2015-10-29 | 2016-01-06 | 中船第九设计研究院工程有限公司 | A kind of hydrogen fluoride recovery and treatment method of electrolysis fluorine tail gas |
| US20190047858A1 (en) * | 2016-02-09 | 2019-02-14 | Central Glass Company, Limited | Method for Purifying Fluorine Gas |
| CN111085081A (en) * | 2019-12-25 | 2020-05-01 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for removing hydrogen fluoride in fluorine gas |
| CN214495731U (en) * | 2021-01-20 | 2021-10-26 | 欧中电子材料（重庆）有限公司 | Device for removing HF in fluorine gas |
-
2021
- 2021-01-20 CN CN202110076695.1A patent/CN114852966B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007301467A (en) * | 2006-05-11 | 2007-11-22 | Hitachi Ltd | Method and apparatus for treating fluorine compound contained in gas |
| CN101423195A (en) * | 2008-11-17 | 2009-05-06 | 袁翔云 | Purification method of fluorine gas |
| WO2012016997A1 (en) * | 2010-08-05 | 2012-02-09 | Solvay Sa | Method for the purification of fluorine |
| CN103079992A (en) * | 2010-08-05 | 2013-05-01 | 索尔维公司 | Method for the purification of fluorine |
| CN102963870A (en) * | 2012-12-11 | 2013-03-13 | 中昊晨光化工研究院有限公司 | Method for purifying fluorine gas |
| CN105214330A (en) * | 2015-10-29 | 2016-01-06 | 中船第九设计研究院工程有限公司 | A kind of hydrogen fluoride recovery and treatment method of electrolysis fluorine tail gas |
| US20190047858A1 (en) * | 2016-02-09 | 2019-02-14 | Central Glass Company, Limited | Method for Purifying Fluorine Gas |
| CN111085081A (en) * | 2019-12-25 | 2020-05-01 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for removing hydrogen fluoride in fluorine gas |
| CN214495731U (en) * | 2021-01-20 | 2021-10-26 | 欧中电子材料（重庆）有限公司 | Device for removing HF in fluorine gas |
Non-Patent Citations (1)
| Title |
|---|
| 柳彤;王少波;董露荣;: "氟化钠吸附氟化氢最佳工艺参数测定", 舰船防化, no. 01, 15 February 2009 (2009-02-15), pages 15 - 20 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650174A (en) * | 2022-11-01 | 2023-01-31 | 福建德尔科技股份有限公司 | Purification device for high-purity fluorine gas |
| CN115650174B (en) * | 2022-11-01 | 2023-08-25 | 福建德尔科技股份有限公司 | Purifying device for high-purity fluorine gas |
| CN115571859A (en) * | 2022-11-10 | 2023-01-06 | 中核四0四有限公司 | Method and device for reducing content of hydrogen fluoride in fluorine gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114852966B (en) | 2024-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106698352B (en) | It is a kind of to prepare high-purity fluorine gas or high-purity method and device containing fluorine mixed gas | |
| CN114852966B (en) | Method and device for removing HF in fluorine gas | |
| CN102101651B (en) | Method and device for refining chlorine hydride byproduct and recovering trifluoromethane in production of monochlorodifluoromethane | |
| CN109999618B (en) | System and method for separating carbon dioxide from medium-high pressure gas source | |
| CN111470478B (en) | High-purity sulfur hexafluoride and preparation method thereof | |
| CN111330412B (en) | System and process for absorbing and purifying byproduct hydrogen chloride gas in chlorination section into acid | |
| CN111085081A (en) | Device and method for removing hydrogen fluoride in fluorine gas | |
| CN109173598B (en) | Method for recovering CS in viscose waste gas by using composite solvent2Method (2) | |
| CN108641023B (en) | Mercury-free polyvinyl chloride production process | |
| CN214495731U (en) | Device for removing HF in fluorine gas | |
| CN112591711B (en) | High-purity high-yield FTrPSA separation and purification extraction method for HF/HCl mixed gas | |
| CN103819306A (en) | Technology for removing ferric trichloride from chlorination liquid generated in chlorobenzene production | |
| CN112661115A (en) | Separation and purification method for deep dehydration and impurity removal of FTrPSA refined by anhydrous HF produced by fluorite method | |
| CN112316713A (en) | System and method for stripping hydrogen from cathode tail gas in nitrogen trifluoride preparation process | |
| CN116555792A (en) | Device and method for producing high-purity deuterium gas by using proton membrane to electrolyze heavy water | |
| CN212215106U (en) | Processing apparatus of synthetic tail gas that produces in amyl anthraquinone production process | |
| CN116081571A (en) | Method and system for recovering hydrogen in chlor-alkali tail gas | |
| CN102584523B (en) | Semifinished chlorinated solution water washing and alkali washing device used during chlorobenzene production and water washing and alkali washing method | |
| CN115305486A (en) | Device and method for preparing high-purity fluorine gas | |
| CN210885864U (en) | System for natural gas system acetylene and hydrogen | |
| CN113996171A (en) | Industrial flue gas desulfurization, denitrification and decarburization system and treatment method | |
| CN112694069A (en) | Method and device for removing free chlorine in waste sulfuric acid | |
| CN216223692U (en) | Chloroethylene purification device | |
| CN210729087U (en) | Carbon dioxide device is handled to chloroethylene synthetic gas | |
| CN220715413U (en) | Chlorination tail gas purification and resource utilization system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |